CN1942398B - Seeded boehmite particulate material and methods for forming same - Google Patents
Seeded boehmite particulate material and methods for forming same Download PDFInfo
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- CN1942398B CN1942398B CN2005800111249A CN200580011124A CN1942398B CN 1942398 B CN1942398 B CN 1942398B CN 2005800111249 A CN2005800111249 A CN 2005800111249A CN 200580011124 A CN200580011124 A CN 200580011124A CN 1942398 B CN1942398 B CN 1942398B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
A boehmite particulate material is disclosed. The material is formed by a process that includes providing a boehmite precursor and boehmite seeds in a suspension, and heat treating the suspension to convert the boehmite precursor into boehmite particulate material. The boehmite particulate material has an aspect ratio of not less than 3:1.
Description
The cross reference of related application
The application is: (i) the part continuation application of the U.S. Patent application of submitting on April 16th, 2,003 10/414590, and 10/414590 is again the non-provisional application of the U.S. Provisional Application 60/374014 submitted on April 19th, 2002; The (ii) part continuation application of the U.S. Patent application of submitting on April 13rd, 2,004 10/823400.The application requires the right of priority of above-mentioned application, and its subject content is incorporated into this by reference.
Background
Invention field
The method of the application's relate generally to boehmite particulate material and this material of formation.The present invention relates more specifically to have seeding (seeded) boehmite particulate material of morphological specificity.
Description of Related Art
Boehmite particulate material can be used as the raw material that formation contains aluminium product such as high-performance alumina abrasive grain especially.Under this background, belong to and disclosed the concrete grammar that forms boehmite particulate material in the United States Patent (USP) 4797139 that this transferee has, this material can be used as the charging that following process forms the stage of alumina abrasive grain subsequently.As described herein, the method (seeded process) that boehmite material is handled by seeding forms, and is confined in the scope of boehmite particulate material adaptation formation alumina abrasive grain.Therefore, the microparticle material that is disclosed has the spherical morphology of special expectation, and this form makes it be applicable to abrasive application.
Except abrasive application, need to produce the boehmite particulate material of various different shapes especially.Because particulate form can produce far-reaching influence to the application of material,, comprise the filler that is used for tailor-(made) coating product and various polymeric articles so constantly increase for the demand that produces the new Material Used except that abrasive material in this area.Other application comprises the state when wherein boehmite material just forms with it rather than those application of using as charging.People are except interested in the generation novel material, and the processing technology that can form this material also must be developed.Thus, this processing technology will have gratifying input-output, can flat-footedly be controlled and high yield can be provided.
General introduction
According to an aspect, the aspect ratio of handling the boehmite particulate material that forms by seeding is not less than 3: 1.
According to another aspect of the present invention, boehmite particulate material forms by the method that may further comprise the steps: the form with suspension provides boeh-mite precursor and boehmite seed, this suspension is carried out heat treated, so that boeh-mite precursor changes into boehmite particulate material.This microparticle material can have certain form, and for example higher aspect ratio for example is not less than about 2: 1, for example is not less than about 3: 1.
In addition, according to another aspect of the present invention, boehmite particulate material forms by the method that may further comprise the steps: the form with suspension provides boeh-mite precursor and boehmite seed, and this suspension is carried out heat treated, so that boeh-mite precursor changes into boehmite particulate material.Herein, boehmite particulate material is made up of thin slice, and its aspect ratio is not less than about 2: 1, for example is not less than about 3: 1.
Brief Description Of Drawings
Fig. 1 is the SEM Photomicrograph of explanation sheet shape boehmite particulate material.
Fig. 2 is the SEM Photomicrograph of explanation needle-shaped boehmite microparticle material.
Fig. 3 is the SEM Photomicrograph of explanation elliposoidal boehmite particulate material.
Fig. 4 is the SEM Photomicrograph of the spherical boehmite particulate material of explanation.
The explanation of preferred implementation
According to an embodiment of the invention; boehmite particulate material forms by the method that may further comprise the steps: the form with suspension provides boeh-mite precursor and boehmite seed; heating (for example; pass through hydrothermal process) this suspension (perhaps colloidal sol or slurry), make boeh-mite precursor change into the boehmite particulate material of particle or crystallite formation.According to a concrete aspect, described boehmite particulate material has elongated relatively form, the general in the text description of using hereinafter described recently in length and breadth.
The general term " boehmite " that uses refers to comprise hydrated aluminum oxide in the literary composition: mineral boehmite is generally Al
2O
3H2O, water content is about 15%; And pseudobochmite (psuedoboehmite), water content is higher than 15 weight %, for example 20-38 weight %.It is to be noted, boehmite (comprising pseudobochmite) has specific and certifiable crystalline structure, thereby the X ray collection of illustrative plates that also has uniqueness, and therefore be different from other alumina-bearing material, comprise other hydrated aluminum oxide, ATH (hibbsite) for example, it is a kind of conventional precursor material that is used to make boehmite particulate material here.
Aspect ratio is defined as longest dimension and ratio perpendicular to the second long size of this longest dimension, generally is not less than 2: 1, preferably is not less than 3: 1,4: 1 or 6: 1.In fact, some embodiment has elongated relatively particle, for example is not less than 9: 1,10: 1, in some cases, is not less than 14: 1.Be particularly related to needle-shaped particles, particle can further recently characterize with second in length and breadth, and second aspect ratio is defined as the ratio of second longest dimension and the 3rd longest dimension.Second aspect ratio generally is not more than 3: 1, is not more than 2: 1 usually, perhaps even 1.5: 1, is about 1: 1 often.Second aspect ratio general description particle cross section geometric form in perpendicular to the plane of longest dimension.
Plate shape or sheet shape particle generally have slim-lined construction, have above in conjunction with the described aspect ratio of needle-shaped particles.But sheet shape particle generally has major surfaces respect to one another, and these opposed major surfaces generally are smooth, and are parallel to each other.In addition, sheet shape particulate feature is second aspect ratio of its second aspect ratio greater than needle-shaped particles, generally is not less than about 3: 1, for example is not less than about 6: 1, perhaps not even less than about 10: 1.Usually, the shortest dimension or the edge dimension perpendicular to opposed major surfaces or face is generally less than 50 nanometers.
The form of boehmite particulate material can be further with granularity, more specifically define with mean particle size.Here, seeded boehmite particulate material is promptly handled the boehmite that (hereinafter will describe in detail) forms by seeding, has thinner granularity or crystallite dimension relatively.Generally speaking, mean particle size is not more than about 1000 nanometers, in the scope of about 100 to 1000 nanometers.Other embodiment has thinner mean particle size, for example is not more than about 800 nanometers, 600 nanometers, 500 nanometers, 400 nanometers, even the particulate mean particle size is represented a kind of fine particles material less than 300 nanometers.
Used term " mean particle size " is used for representing the mean value of the longest dimension of particulate or length in the literary composition.Because particle is an elongated condition, conventional characterization technique generally is not enough to measure mean particle size, because characterization technique is a spheric or subsphaeroidal based on the hypothesis particle usually.Therefore, determine mean particle size by the granularity of selecting a plurality of representative samples also physically to measure these representative samples.This class sample can be selected by various characterization technique such as scanning electronic microscope (SEM).
Discover that seeded boehmite particulate material of the present invention has tiny mean particle size, and the technology based on non-seeding processing (non-seeded) of normal competition with it generally can not provide tiny like this mean particle size.Thus, be noted that the granularity of usually being reported in the literature is not to state with mean value same in this specification sheets, but be described as the granularity nominal range that obtains by physical detection microparticle material sample.Therefore, in the scope that mean particle size will drop in the prior art to be reported, for Gauss's size-grade distribution of expection, generally about the arithmetic mid point of report scope.Perhaps in other words, though can report fine granularity based on non-seeding treatment technology, this fine size refers generally to the lower value of the granularity observed, rather than the mean particle size value.
Equally, in a similar fashion, more than Bao Dao aspect ratio is generally corresponding to the average aspect ratio that is obtained by representative sample, rather than the upper limit or the lower value that are associated with the microparticle material aspect ratio.Usually the particle aspect ratio of report is not to state with the same mean value of this specification sheets in the literature, but is described as the aspect ratio nominal range that obtains by the physical detection particulate samples.Therefore, in the scope that average aspect ratio will drop in the prior art to be reported, distribute, generally about the arithmetic mid point of report scope for Gauss's particle form of expection.Perhaps in other words, can report aspect ratio, but this data generally are meant the lower value of the distribution of aspect ratios that observes based on the technology that non-seeding is handled, rather than the average aspect ratio value.
Except the aspect ratio and mean particle size of microparticle material, can further come the form of characterizing particles material according to specific surface area.Here, the specific surface area that normal available BET technology is measured microparticle material is passed through in use.According to the embodiment described in the literary composition, boehmite particulate material has higher specific surface area, is not less than about 10 meters squared per gram usually, for example is not less than about 50 meters squared per gram, 70 meters squared per gram or is not less than about 90 meters squared per gram.Because specific surface area becomes with particle form and granularity, so the specific surface area of all embodiments is generally less than about 400 meters squared per gram, for example less than about 350 or 300 meters squared per gram.
Go through the method that can be used to make boehmite particulate material again, roughly the boehmite particles of elliposoidal, aciculiform or sheet shape with boeh-mite precursor (alumina-bearing material that normally comprises bauxite material) through hydrothermal process and forming, as described in the above-mentioned total United States Patent (USP) 4797139.More specifically, boehmite particulate material can form by following steps: boeh-mite precursor is mixed in suspension with boehmite seed, make this suspension (perhaps colloidal sol or slurry) accept thermal treatment, impelling feedstock conversion is boehmite particulate material, and the influence of the boehmite seed that provides in the suspension is provided in addition.Heating is to carry out in the autoclave at spontaneous environment generally, and therefore pressure raises in this process.The pH value of suspension is chosen in less than 7 usually or greater than 8 numerical value, the granularity of boehmite seed material is less than about 0.5 micron.Generally speaking, among the present invention the amount of seed particles greater than 1 weight % of boeh-mite precursor (with Al
2O
3Calculate).Heating about 120 ℃, for example greater than about 125 ℃ or even greater than about 130 ℃ temperature, greater than about 85psi, for example greater than about 90psi, 100psi or even greater than carrying out under the pressure of about 110psi.
Can make microparticle material under the condition in conjunction with low crystal seed amount and acid ph value again at long-time hydrothermal solution environment, the result makes boehmite along a crystallographic axis or two crystallographic axis preferred growths.In general, the hydrothermal process of long period can be used for producing boehmite particles long, that aspect ratio is higher and/or overall bigger particle.
After thermal treatment (for example passing through hydrothermal process) and boehmite conversion, generally remove liquid substance by for example ultrafiltration process or by thermal treatment evaporation remaining liq.After this, generally the gained material is pulverized, for example reach 100 orders.What be noted that particle size general description described here is the single crystallite that forms by handling, rather than stays aggregate (for example, those are called the product of aggregate material) in some embodiments.
According to the data that the inventor collects, can in the process of handling boehmite raw materials, do some and adjust, to realize required form to some variablees.These variablees comprise with attracting people's attention weight ratio be boeh-mite precursor with the ratio of boehmite seed, treating processes in the temperature (it is directly proportional with pressure in the Self-heating pendular ring border) of the particular type of used acid or alkali or kind (and relative pH value) and system.
Especially, when keeping other variable constant when changing weight ratio, the coating of particles and the size that form boehmite particulate material change.For example, when processing be 180 ℃, in the salpeter solution of 2 weight %, with 90: 10 ATH: the boehmite seed ratio was carried out 2 hours, formed needle-shaped particles (ATH is a species of boehmite precursor).On the contrary, as ATH: when the boehmite seed ratio reduces to 80: 20, coating of particles become more near ellipsoid some.And when this ratio further reduced to 60: 40, particle became subsphaeroidal.Therefore, most typical is that the ratio of boeh-mite precursor and boehmite seed is not less than about 60: 40, for example is not less than about 70: 30 or 80: 20.But to promote forming required fine particles form, the weight ratio of boeh-mite precursor and boehmite seed generally is not more than about 98: 2 in order to ensure enough seeding levels (seedingleve1).According to the above, the increase of aspect ratio is generally followed in the increase of weight ratio, and reducing of aspect ratio generally followed in the minimizing of weight ratio.
In addition, when keeping other variable constant when the type that changes acid or alkali, coating of particles (for example, aspect ratio) and size also can be affected.For example, when processing be 100 ℃, with ATH: boehmite seed is 90: 10 ratio, when carrying out in the salpeter solution of 2 weight %, institute's synthetic particle generally is an aciculiform, on the contrary, when nitric acid is 1 weight % or when replacing less than the HCl of 1 weight %, institute's synthetic particle generally is subglobose by concentration.When working concentration was equal to or greater than the HCl of 2 weight %, institute's synthetic particle generally became aciculiform.For the formic acid of 1 weight %, institute's synthetic particle is a sheet shape.In addition, use alkaline solution, the KOH of 1 weight % for example, then institute's synthetic particle is a sheet shape.If use the mixture of bronsted lowry acids and bases bronsted lowry, the nitric acid of the KOH of 1 weight % and 0.7 weight % for example, then synthetic particulate form is a sheet shape.
Suitable bronsted lowry acids and bases bronsted lowry comprises: mineral acid, for example nitric acid; Organic acid, for example formic acid; Contain hydracid, for example hydrochloric acid; And acid-salt (acidic salt), for example aluminum nitrate and sal epsom.Effectively alkali comprises: for example, amine comprises ammonia; Alkali metal hydroxide, for example potassium hydroxide; Alkaline hydrated oxide, for example calcium hydroxide; And basic salt (basic salt).
And when keeping other variable constant when changing temperature, obvious variation can take place in granularity usually.For example, when processing is with ATH: boehmite seed is 90: 10 ratio, in the salpeter solution of 2 weight %, carried out two hours at 150 ℃, and obtaining crystalline size by XRD (X-ray diffraction characterization) is 115 dusts.But 160 ℃ of processing, mean particle size is 143 dusts.Therefore, along with temperature raises, granularity also increases, and shows the relation in direct ratio between granularity and the temperature.
Embodiment 1, and sheet shape particulate is synthetic
The nitric acid that in autoclave, adds boehmite, 66.5 pounds of deionized waters, 0.037 pound of potassium hydroxide and 0.18 pound of 22 weight % that 7.42 pounds of Hydra1710 aluminium hydroxides of buying from Alcoa, 0.82 pound buy with name of an article Catapal B pseudobochmite from SASOL.Earlier boehmite is pre-dispersed in 5 pounds of water and the 0.18 pound of acid, joins again in aluminium hydroxide and remainder water and the potassium hydroxide.
Under the 530rpm rotating speed stirred, autoclave was at 45 minutes internal heating to 185 ℃, and this temperature maintenance 2 hours.Spontaneous pressure reaches about 163psi, and remains on this pressure.Then, the boehmite dispersion is taken out from autoclave.After autoclave was handled, the pH of colloidal sol was about 10.Remove liquid substance at 65 ℃.The gained material is pulverized less than 100 orders.The SSA of gained powder is about 62 meters squared per gram.
Embodiment 2, needle-shaped particles synthetic
The nitric acid of the boehmite that the Hydra1710 aluminium hydroxide that adding 250 grams are buied from Alcoa in autoclave, 25 grams are buied with name of an article Catapal B pseudobochmite from SASOL, 1000 gram deionized waters and 34.7 grams 18%.Boehmite is pre-dispersed in the acid of 100 gram water and 6.9 grams earlier, joins again in aluminium hydroxide and remainder water and the acid.
Under the 530rpm rotating speed stirred, autoclave was at 45 minutes internal heating to 180 ℃, and this temperature maintenance 2 hours.Spontaneous pressure reaches about 150psi, and remains on this pressure.Then, the boehmite dispersion is taken out from autoclave.After autoclave was handled, the pH of colloidal sol was about 3.Remove liquid substance at 95 ℃.The gained material is pulverized less than 100 orders.The SSA of gained powder is about 120 meters squared per gram.
Embodiment 3, ellipsoidal particle synthetic
The nitric acid of the boehmite that the Hydra1710 aluminium hydroxide that adding 220 grams are buied from Alcoa in autoclave, 55 grams are buied with name of an article Catapal B pseudobochmite from SASOL, 1000 gram deionized waters and 21.4 grams 18%.Earlier boehmite is pre-dispersed in 100 gram water and the 15.3 gram acid, joins again in aluminium hydroxide and remainder water and the acid.
Under the 530rpm rotating speed stirred, autoclave was at 45 minutes internal heating to 172 ℃, and this temperature maintenance 3 hours.Spontaneous pressure reaches about 120psi, and remains on this pressure.Then, the boehmite dispersion is taken out from autoclave.After autoclave was handled, the pH of colloidal sol was about 4.Remove liquid substance at 95 ℃.The gained material is pulverized less than 100 orders.The SSA of gained powder is about 135 meters squared per gram.
Embodiment 4, and subsphaeroidal particulate is synthetic
The nitric acid of the boehmite that the Hydra1710 aluminium hydroxide that adding 165 grams are buied from Alcoa in autoclave, 110 grams are buied with name of an article Catapal B pseudobochmite from SASOL, 1000 gram deionized waters and 35.2 grams 18%.Earlier boehmite is pre-dispersed in 100 gram water and the 30.6 gram acid, joins again in aluminium hydroxide and remainder water and the acid.
Under the 530rpm rotating speed stirred, autoclave was at 45 minutes internal heating to 160 ℃, and this temperature maintenance 2.5 hours.Spontaneous pressure reaches about 100psi, and remains on this pressure.Then, the boehmite dispersion is taken out from autoclave.After autoclave was handled, the pH of colloidal sol was about 3.5.Remove liquid substance at 95 ℃.The gained material is pulverized less than 100 orders.The SSA of gained powder is about 196 meters squared per gram.
According to the embodiment described in the literary composition, more effectively and flexibly method can be with making the boehmite product with final have required form.The particularly important is, described embodiment uses seeding to handle, and obtains a kind of high investment output and can highly control the processing approach for the treatment of processes, can finally obtain required mean particle size and in check size-grade distribution.With following the two combination is particularly important: (i) key variables in affirmation and the control method, for example type of weight ratio, bronsted lowry acids and bases bronsted lowry and temperature; (ii), provide repeating and controllable processing to required boehmite particulate material form based on the technology of seeding.
Aspects of the present invention can use in many application boehmite particulate material, for example the filler of tailor-(made) coating and polymeric articles.In fact, can make microparticle material separately and be evenly dispersed in solvent (especially comprising polar solvent) and/or the polymkeric substance by the method for compounding of routine, and not form aggregate.In addition, can utilize conventional dispersion agent such as silane coupling agent to make boehmite particulate material separately and be evenly dispersed in non-carrying out in solvent and/or the polymkeric substance, and not form aggregate.Certainly, the concrete application of boehmite particulate material is unrestricted, can be used in many application in commerce.
Though describe the present invention in the embodiment and describe in explanation, the present invention is not subject to these and describes in detail,, can carry out various modifications and substitute because under the prerequisite that deviates from the scope of the invention by any way.For example, other or the surrogate that is equal to can be provided, perhaps the production stage that is equal to can be used.Like this, those skilled in the art can only use normal experiment that the present invention who is disclosed in the literary composition is carried out other variation and be equal to, and all these variations and being equal to it is believed that in the scope of the present invention that limits in claims.
Claims (9)
1. method that forms boehmite particulate material, it comprises:
Form with suspension provides boeh-mite precursor and boehmite seed, and the weight ratio of boeh-mite precursor and boehmite seed is not less than 60: 40;
In the temperature that is higher than 120 ℃ described suspension is heat-treated, so that boeh-mite precursor is converted into boehmite particulate material, mainly by sheet shape granulometric composition, its aspect ratio is not less than 3: 1 to described boehmite particulate material, and its second aspect ratio is not less than 3: 1,
Described method is carried out in the mixture of formic acid, KOH or KOH and nitric acid.
2. the method for claim 1 is characterized in that, described thermal treatment is carried out in the temperature that is higher than 130 ℃.
3. the method for claim 1 is characterized in that, described thermal treatment is carried out being higher than under the pressure of 85psi.
4. the method for claim 1 is characterized in that, described weight ratio is not less than 80: 20.
5. method as claimed in claim 4 is characterized in that the weight ratio of described boeh-mite precursor and boehmite seed is not more than 98: 2.
6. the method for claim 1 is characterized in that, the mean particle size of described boehmite particulate material is not more than 1000 nanometers.
7. the method for claim 1 also comprises at least one that is provided with in the following condition so that the mean particle size of boehmite particulate material is not more than 1000 nanometers: the weight ratio of thermal treatment temp or boeh-mite precursor and boehmite seed.
8. method as claimed in claim 7 is characterized in that, the ratio that improves boeh-mite precursor and boehmite seed perhaps reduces described ratio to reduce aspect ratio to increase aspect ratio.
9. method as claimed in claim 7 is characterized in that, improves thermal treatment temp to increase granularity, perhaps reduces thermal treatment temp to reduce granularity.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/823,400 US20050227000A1 (en) | 2004-04-13 | 2004-04-13 | Surface coating solution |
US10/823,400 | 2004-04-13 | ||
US10/845,764 US20040265219A1 (en) | 2002-04-19 | 2004-05-14 | Seeded boehmite particulate material and methods for forming same |
US10/845,764 | 2004-05-14 | ||
PCT/US2005/012038 WO2005100244A2 (en) | 2004-04-13 | 2005-04-12 | Seeded boehmite particulate material and methods for forming same |
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CN1942398A CN1942398A (en) | 2007-04-04 |
CN1942398B true CN1942398B (en) | 2010-11-10 |
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CN201310295835XA Pending CN103396690A (en) | 2004-04-13 | 2005-04-12 | Surface coating solution |
CN2005800111249A Active CN1942398B (en) | 2004-04-13 | 2005-04-12 | Seeded boehmite particulate material and methods for forming same |
CNA2005800109766A Pending CN1942534A (en) | 2004-04-13 | 2005-04-12 | Flame retardant composites |
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CN201310295835XA Pending CN103396690A (en) | 2004-04-13 | 2005-04-12 | Surface coating solution |
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US (1) | US20050227000A1 (en) |
EP (1) | EP1735390A2 (en) |
JP (1) | JP2007532756A (en) |
KR (1) | KR100855896B1 (en) |
CN (3) | CN103396690A (en) |
AT (1) | ATE517846T1 (en) |
AU (1) | AU2005233613B2 (en) |
BR (1) | BRPI0509907A (en) |
CA (1) | CA2562906C (en) |
ES (1) | ES2375451T3 (en) |
IL (2) | IL178625A0 (en) |
MX (1) | MXPA06011804A (en) |
NO (1) | NO20065177L (en) |
NZ (2) | NZ550507A (en) |
RU (2) | RU2342321C2 (en) |
UA (2) | UA88296C2 (en) |
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- 2005-04-12 AU AU2005233613A patent/AU2005233613B2/en not_active Ceased
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UA91502C2 (en) | 2010-08-10 |
ES2375451T3 (en) | 2012-03-01 |
RU2342321C2 (en) | 2008-12-27 |
CN1942534A (en) | 2007-04-04 |
WO2005100491A3 (en) | 2005-12-22 |
WO2005100491A2 (en) | 2005-10-27 |
AU2005233613A1 (en) | 2005-10-27 |
IL178621A (en) | 2012-08-30 |
CN103396690A (en) | 2013-11-20 |
RU2006136225A (en) | 2008-05-20 |
IL178625A0 (en) | 2007-02-11 |
AU2005233613B2 (en) | 2008-02-21 |
JP2007532756A (en) | 2007-11-15 |
RU2006136226A (en) | 2008-05-20 |
CA2562906C (en) | 2010-12-21 |
US20050227000A1 (en) | 2005-10-13 |
RU2396298C2 (en) | 2010-08-10 |
KR100855896B1 (en) | 2008-09-03 |
EP1735390A2 (en) | 2006-12-27 |
NO20065177L (en) | 2006-12-01 |
NZ550507A (en) | 2010-05-28 |
MXPA06011804A (en) | 2007-01-26 |
UA88296C2 (en) | 2009-10-12 |
ZA200608537B (en) | 2008-06-25 |
IL178621A0 (en) | 2007-02-11 |
KR20060134207A (en) | 2006-12-27 |
NZ550508A (en) | 2010-12-24 |
ZA200608451B (en) | 2008-08-27 |
CN1942398A (en) | 2007-04-04 |
ATE517846T1 (en) | 2011-08-15 |
CA2562906A1 (en) | 2005-10-27 |
BRPI0509907A (en) | 2007-09-18 |
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